Synthesis of ultrafine rutile phase titanium dioxide particles

ABSTRACT

The present invention provides a low temperature process for the synthesis of ultrafine rutile phase titanium dioxide particles through vapor phase hydrolysis of titanium tetra chloride.

FIELD OF THE INVENTION

The present invention relates to a low temperature process for the synthesis of ultrafine rutile phase titanium dioxide particles through vapor phase hydrolysis of titanium tetra chloride. In particular the present invention relates to a method for the manufacture of rutile grade titanium dioxide powder using ethanol as dopant to bring down the rutile formation temperature to as low as 150-400° C. during calcination with time duration of 1 to 4 hrs. The process includes a novel combination of operational steps to economically produce ultrafine titanium dioxide powders of rutile phases in a flexible manufacturing process.

BACKGROUND OF THE INVENTION

Titanium dioxide (titania) is extensively used as pigments, catalysts, inorganic membranes, semi-conductors, optical coating reagent and as photocatalysts in water purification process. Titanium dioxide (TiO₂) has two phases of crystalline structure of industrial importance, namely, anatase and rutile. Titanium dioxide with anatase phase has been used as a photocatalyst for photodecomposition of acetone, phenol or trichloro ethylene, oxidation such as nitrogen mono-oxide and hitrogen dioxide and conversion system using solar energy due to its high photo-activity. Titanium dioxide with rutile phase has been widely used as white pigment because of its good scattering effect that protects the ultraviolete light. It has also been used in optical coatings, beam splitter and anti-reflection coatings since it has a high dielectric constant and high refractive index, good oil absorption ability, tinting power and chemical stability even under strongly acidic or basic conditions. Titanium dioxide shows different electrical characteristics according to oxygen partial pressure since it has wide chemical stability and non-stoichiometric phase region. Because of this, it can also be used as a humidity sensor and as high-temperature oxygen sensor and the field of its use has become wide.

Titanium dioxide powders for pigment use generally have an average particle size of 150 to 250 nanometer and is considered the principal white pigment of commerce. It has an exceptionally high refractive index, negligible color and is quite inert. Titanium dioxide is having a smaller average particle size, for instance in the 10 to 100 nanometer median particle size range, is used commercially in cosmetics and personal care products, plastics, surface coating, self—cleaning surfaces, and photo voltaic applications. This grade of titanium dioxide is referred to as ultrafine or nano-sized titanium dioxide. More than four million tons of titanium dioxide are produced annually; there are several processes for making ultrafine titanium dioxide, some in commercial use and some in development. Some use anhydrous titanium dioxide, some in commercial use and some in development. Some use anhydrous titanium tetrachloride as a feed stock. Another process use a titanyl sulfate solution as the feed stock.

Generally, titanium dioxide powders are manufactured by a chloride process, which is a gas phase process, or by a sulfate process, which is a liquid phase process.

In the chloride process, which was commercialized by Du Pont of USA in 1956, titanium tetrachloride, is used as a starting material and the reaction temperature needs to be higher than 1,000° C. This method also requires extra protection devices because of the corrosive Cl₂ gas product at high temperature in the process, leading to higher production costs. Because titanium dioxide powders produced by the chloride process are fine but rough, additive equipment for providing external electrical fielfs or controlling reactant mixing ratios are required to control the particle shape and the particle size of titanium dioxide powders. High pure oxygen is required for oxidation of TiCl₄ and that leads to high capital and operating costs.

In the sulfate process, which was commercialized by Titan company of Norway in 1961, titanium sulfate (TiSO₄) is conventionally hydrolyzed at temperatures higher than 100° C., calcined at 800-1000° C. and then pulverised to produce titanium dioxide powders. During the calcination and pulverization processes, impurities are introduced causing the quality of the final titanium dioxide powder to be low.

Funaki, Saeki, et al. in Kogyo Kagaku Zasshi, 59 (11), pp. 1291 (1956), teach that fine particles of anatase-type titanium dioxide can be produced by mixing titanium tetrachloride and water in the vapor phase at a temperature in the range from 200° C. to 800° C. or fine particles of anatase-type titanium dioxide containing or not containing a very small amount of rutile-type particles can be produced by the reaction of titanium tetrachloride and water in the liquied phase and a much higher temperature treatment to obtain rutile phase titanium dioxide.

A method for preparing spherical particles of a metal oxide comprising hydroysis of a hydrolysable titanium (IV) compound in the form of a liquid aerosol by being contacted with water vapor in a dynamic flow is taught in U.S. Pat. No. 4,241,042. A method in which a precursor of a metal oxide in the form of a very fine droplet suspension of the liquid is heated and gasified by evaporation and thermal decomposition and then contacted and reacted with an oxygen containing gas in the vapor phase to give spherical fine particles of a metal oxide is taught in Japanese Patent Kokai 59-107904 and 59-107905.

Recently considerable interest has been directed toward the synthesis of rutile grade titania at low temperature. There have been some reports about new liquid phase processes to synthesis of rutile grade titanium dioxide powder using titanium tetrachloride. Kim, Park et al, (U.S. Pat. No. 6,001,326) show new liquid phase process in which Tio₂ precipitates with pure rutile phase having spherical shapes having 200-400 mm in diameter formed between room temperature and 65° C., by the homogeneous precipitation method simply by heating and stirring an aqueous TiOCl₂ solution.

Tang et al., (Mater. Chem. Phys. 77 (2): pp. 314, (2003) disclose the preparation of nanosized rutile TiO₂ powder by hydrolysis of Ti (OC4H₉) 4 solution at 40-50° C. When the solution is neutral and basic, the hydrolysis product is a precipitate and the dried precipitte is amorphous. The rutile phase TiO₂ cannot be obtained even when the dried precipitate is calcined at 600° C. However, when the solution is acidic, the hydrolysis product is a sol, in order to obtain rutile TiO₂ by drying the gel at 40-50° C. However, tight control of reaction conditions is required, since alkoxide is intensely hydrolyzed in air. Furthermore, he high price of the alkoxide limits its commercialization.

Yang et al., (Mater. Chem. Phys., 77 (2): pp. 501, (2003) also reported that titania nanocrystals in the rutile form were prepared in liquid phase at room temperature under normal pressure. Li Y.Z. et al, also reported in Jour. Mater. Chem., 12 (5): pp. 1387, (2002), the preparation of nano-crystalline rutile TiO₂ with average crystal sizes of 6.9-10.5 nm by hydrolysis of TiCl₄ aqueous solution at lower temperatures. All the above reported techniques of synthesizing rutile phase titanium dioxide are based on liquid phase processing.

In comparison with liquid phase routes, vapor phase hydrolysis of titanium chloride to synthesize anatase has been reported. For example; B. Xia et al. (Jour. Mater. Sci., 34, pp. 3505, (1999), reported the preparation of anatase TiO₂ nanopowders by vapor-phase hydrolysis of TiCl₄ below 600° C. As an independent preparation route, it hasn't been paid much attention.

Compared with liquid phase process, the vapor phase process carried out in an aerosol reactor offers many advantages including product purity, ease of collection, energy efficiency and avaoids treatment like filtration, washing drying etc., involving large liquid volumes. However, the chloride process is carried out at high temperature and has encountered several problems such as control of product characteristics, corrosion of reactor material of construction and operational problems, mainly due to the high temperatures and corrosive gases involved. Therefore, there is a need for a process to produce ultrafine titanium dioxide at temperature much reduced from those encountered in the chloride process but involving only gas phse processing without involvement of liquids.

OBJECTS OF THE INVENTION

The main objective of the invention is to develop a low temperature process for the synthesis of ultrafine rutile particles through vapor phase hydrolysis of TiCl₄.

Another object of the present invention is to develop a flexible low temperature process for the synthesis of anatase, rutile and mixtures thereof in the same reactor system.

SUMMARY OF THE INVENTION

The present invention provides a low temperature process for the synthesis of ultrafine rutile phase titanium dioxide particles through vapor phase hydrolysis of titanium tetrachloride comprising the step of:

-   a) hydrolyzing a mixture of TiCl₄ and H₂O and a dopant in vapour     phase in an aerosol reactor; -   b) collecting amorphous or anatase titanium dioxide powder formed as     dry powders; -   c) calcining the dry powder to obtain rutile phase titanium dioxide.

In one embodiment of the invention, the amorphous particles of titanium dioxide are calcined at a temperature in the range of 150 to 400° C. and for a period in the range of 1 to 4 hrs to generate rutile particles.

In another embodiment of the invention, the dopant contains a carbon atom and is selected from the group consisting of an aliphatic alcohol, an aromatic hydrocarbon, and any mixture thereof

In yet another embodiment of the invention, the dopant is ethanol.

In yet another embodiment of the invention, the molar concentration of the dopant is 1 to 10 based on the water vapour.

In another embodiment of the invention, the reaction mixture contains from 0 to 10% ethanol on a molar basis based on TiCl₄.

In another embodiment of the invention, the flow rate of TiCl₄ is in the range of 10 cm³/min to 200 cm³/min.

In yet another embodiment of the invention, the TiCl₄ vapor concentration inside the reactor is in the range of 7×10⁻⁴ mol/min to 1×10⁻² mol/min.

In yet another embodiment of the invention, the flow rate of water vapour is in the range of 240 to 1500 cm³/min, preferably from 500 to 1000 cm³/min.

In one embodiment of the invention, temperature at the exit of the aerosol reactor is maintained at less than 100° C. for obtaining titanium dioxide particles having anatase phase.

In another embodiment of the invention, the aerosol reactor is externally heated in order to avoid particle coating on the walls through thermophoresis.

In yet another embodiment of the invention, the aerosol reactor consists of 3-tube concentric jet assembly wherein TiCl₄ is introduced into the innermost tube, dopant is introduced into the outermost tube and water vapor is introduced into the middle tube.

In another embodiment of the invention, the 3-tube assembly comprises a concentric arrangement of three inconel tubes at the entrance of the aerosol reactor.

In another embodiment of the invention, the vapor phase TiCl₄ is introduced into a center tube of the three concentric inconel tubes.

In another embodiment of the invention, the vapor phase TiCl4 is formed by bubbling an inert gas through TiCl₄ liquid.

In a further embodiment of the invention, the inert gas is selected from the group consisting of argon, nitrogen, krypton, helium and any mixture thereof

In yet another embodiment of the invention, the molar ratio of water to titanium tetra chloride in the feed is in the range 10 to 15.

In another embodiment of the invention, the water vapor is formed by bubbling air or inert gases through water under superheated condition.

In another embodiment of the invention, the reactor wall temperature is from 200 to 450° C.

In yet another embodiment of the invention, the rutile titanium dioxide particles formed have an average diameter in the range of from 25 to 150 nanometers.

The present invention also provides a low temperature process for the synthesis of ultrafine rutile phase titanium dioxide particles through vapor phase hydrolysis of titanium tetrachloride comprising the step of:

-   a. vaporizing a titanium chloride liquid, water and a dopant     comprising ethanol separately to generate a reaction mixture; -   b. hydrolyzing vapor phase TiCl₄ and H₂O and dopant mixture in a     continuous aerosol reactor under non-isothermal conditions at a     temperature in the range of 80 to 135° C.; -   c. collecting amorphous and anatase phase titanium dioxide powder as     dry powder; -   d. Calcining the titanium dioxide particles having amorphous phase     at a temperature range of 150-400° C. and for a period in the range     of 1 to 4 hrs to obtain titanium dioxide particles with rutile     phase.

BRIEF DESCRIPTION OF THE DRAWING

In the drawings accompanying this specification

FIG. 1 represents a flow sheet of the general aspect of the rutile phase titanium dioxide synthesis using low temperature vapore phase process according to the present invention.

FIG. 2 represents a layout of nozzle inlet assembly for mixing of reactants of reactants and dopant in the inlet part to the reactor.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a gas phase based aerosol synthesis of rutile phase titanium dioxide particles at a much lower temperature so as to avoid the several unit operations for the treatment of large liquid volumes and non-requirement of a need for high purity oxygen as in the chloride process. The present invention has successfully led high purity oxygen as in the chloride process. The present invention has successfully led to the development of to new titanium dioxide powder manufacturing method. In this method, it is possible to prepare ultrafine titanium dioxide powders of rutile phase continuously with excellent control of particle characteristics such s particle shase, particle size, and specific crystallographic modifications. This invention also provides a low temperature, low cost, environmentally friendly flexible process for preparing titanium dioxide powders. In addition, it is easy to control the mixture ratio of rutile and anatase phase of the titanium dioxide crystallites.

The present invention relates to a process for the synthesis of titanium dioxide powders having rutile phase by TiCl₄ hydrolysis in vapor phase followed by low temperature calcination. The process defined herein consists of three basis steps:

-   (1) Hydrolyzing a reactant mixture containing TiCl₄ vapor, water     vapor and optionally a dopant in a vapour phase reactor. -   (2) Collecting titanium dioxide powder having amorphous phase formed     inside the vapor phase reactor. -   (3) Low temperature calcination of the collected powder.

The precise details of these steps are set forth below. Although specific executions and examples are discussed in this application, it is envisioned that the present invention encompasses the full range of obvious variants of those specifically disclosed herein.

Hydrolyzing Step

The hydrolyzing reaction takes place in the aerosol reactor of ID 2.5 cm and 1.5 m in length, heated externally in a horizontal electrical furnace (FIG. 1). The reactor comprises of a metallic tube made of Inconel in which the reactants (TiCl₄, H₂O, and the dopant) are introduced as vapor. The aerosol reactor consists of three concentric Inconel tubes as shown in FIG. 2 the inner diameter of the central tube is 2 mm and the spacing between successive tubes is 1 mm respectively. The mixture of TiCl₄ vapor and nitrogen is introduced through the concentric inconel tube (a), water vapor is introduced through the tube (b) and dopant vapor is introduced into the system through the concentric inconel tube (c).

The TiCl₄ reactant is introduced into the reactor in the vapor phase. In this invention TiCl₄ vapor can be generated by bubbling an inert gas through liquid TiCl₄, the nitrogen gas/TiCl₄ vapor is preferably directed through the concentric inconel tube (a) of the reactor. The TiCl₄ flow rates utilized in the process of the present invention are generally from about 10 cm³/min to about 200 cm³/min. This flow rate (together with the liquid TiCl₄ temperature) essentially define the concentration of TiCl₄, which is present inside the reactor. The TiCl₄ vapor concentration ranges inside the reactor, which are useful in the present invention, are from about 7×10⁻⁴ mol/min to about 1×10⁻² mol/min. Heating the TiCi₄ liquid through which the nitrogen gas is bubbled controls the actual concentration of TiCl₄ vapor in the nitrogen gas. The higher the temperature utilized, the greater the TiCl₄ vapor concentration achieved. In this regard, it is preferred that the TiCl₄ through which the nitrogen is bubbled has a temperature of from about 20° C. to about 100° C.

The other required reactant utilized in the process of the invention is water vapor. Water vapor is generated by bubbling air through water and directing that gas (air with water vapor) into the reactor through the concentric inconel tube (b). This procedure allows for precise control of water vapour flow rate and concentration in the reactor. The air (containing water vapour) flow rate is generally from about 240 to about 1500 cm³/min, preferably from about 500 to about 1000 cm³/min. The reaction mixture, which is utilized in the present invention also, includes a dopant material, in vapor phase, it positively affect the physical attributes of the titanium dioxide formed. The TiCl₄ reactant, water vapor and the dopant may be mixed in the reactor. It is preferred that the dopant vapor be introduced through the concentric inconel tube (c). Aliphatic alcohols, aromatic hydrocarbons and mixtures thereof can be used as dopants out of which ethanol is used for this present invention. In selecting the amount of dopant to the used in the process, it is generally advisable to use dopant molar concentration in the range one to ten percent of the concentration of water vapor.

Reaction

In chemical terms, the reactions being carried out in the present invention are as follows: TiCl₄+4 H₂O→Ti(OH)₄+4 HCL Ti(OH)₄→TiO₂+2H₂O

The size range of particles formed due to the above reactions can be controlled by reaction temperature and molar ratio of H₂O/TiCl₄ in the reactor.

Separation of Titanium Dioxide Particle from Gas Phase

The TiO₂ particles formed are either amorphosuse or anatase and this powder is collected on a bag filter, made of Teflon which is aided by vacuum pump. The filter bag is maintained at temperatures in the range 130 to 140° C. to avoid condensation.

Calcination

The titanium dioxide powder having amorphous phase resulting from gas phase hydrolysis of titanium chloride without dopant is calcined at a temperature in the range of 300-600° C. and for a length of time in the range of 1-4 hours to obtain rutile phase or mixtures there of with anatase phase. In the presence of a vapor phase dopant such as ethanol during the gas phase hydrolysis, the rutile formation temperature is reduced to as much as 150-400° C. compared to other usual calcination treatments, and the calcination duration is also sufficiently shortened to limit the excessive particle growth through sintering. In comparison in the absence of dopant during the hydrolysis step, calcination temperature can range between 800° C. to 1100° C. in the gas phase hydrolysis for anatase to rutile transformation. In the presence of dopant, anatase to rutile transformation takes place during the vapor phase hydrolysis, calcinations temperature range can be reduced between 500 to 700° C.

The following illustrative examples are not intended to restrict the scope of the present invention. The following examples also illustrate the unique advantage of using dopants during the hydrolysis in the process of this invention.

-   Example 1 illustrates the vapor phase hydrolysis of TiCi₄ and water     without any dopant to synthesize titania nanopowders having the     urtile phase. -   Example 2 illustrates the vapor phase hydrolysis of TiCl₄ and water     with dopant as ethanol to synthesize titania nanopowders having the     rutile phase.

EXAMPLE 1

Dry nitrogen (99.9%) is bubbled through a gas bottle containing titanium etrachloride (commercial grade) maintained at a temperature of 90° C. and is directed through the central tube of the aerosol reactor. Concentration of TiCl₄ in the gas stream is determined by recording the weight of TiCl₄ before and after each experiment. A constant N₂ flow rate of 500 cm³/min through the TiCi4 bubbler is used. The corresponding molar flow rate of TiCl₄ is 1.7 ×10⁻³ mol/min. Air is bubbled through a gas washed bottle containing water (temperature=90° C.) and is directed through the second tube of the nozzle distributor. Mass flow controllers (1259 B, MKS) precisely control all flows into reactor. The TiCl₄ vapor and the water vapor are mixed rapidly around the nozzle and form TiO₂ aerosol at near atmospheric pressure. Titanium dioxide particles produced by gas phase hydrolysis of TiCl₄ in the aerosol reactor are collected in a bag filter made of Teflon. The titanium dioxide powder is obtained directly as dry powders for characterization. The exhoust gas is completely absorbed by a set of bubblers. Portions of the powders produced were heat treated in a conventional muffle furnace. Powder was calcined at 800° C. for 3 hrs. Rotameter is used for measuring the flow rate of air.

TiO₂ is synthesized (without the use of dopants), in this example, the following range of reaction conditions is utilized.

-   Inlet gas stream temperature=70-80° C. -   Exit gas stream temperature=130-150° C. -   Air flow rate=1000.00 cm³/min. (STP) -   TiCl₄ molar flow rate=1.7×10⁻³mol/min. -   H₂O/TiCl₄ molar ration=15

Phase composition of collected particles was determined by X-ray diffraction (XRD) in a Philips Holland Exper-Pro diffractometer operating at 40 kV, 20 mA, using CuK_(α)Radiation. Weight fractions of the rutile and anatase phases in samples are calculated from the relative intensities of strongest peaks corresponding to anatase (2θ=25.6 for the (101) reflection of anatase) and rutile (2θ=27.5 for the (110) reflection of rutile) peaks as described by Spurr and Myers, Quantitative Analysis of Anatase-Rutile Mixture with an X-ray Diffractometer, Analytical Chem., 29: 760 (1957). Specific surface area of the powders is measured using a BET Nitrogen adsorption apparatus (Gemini 2375 V4.02). Scanning Electron Microscopy SEM-JIOL: 1.5 kV) is used for morphological analysis of the powders.

Titanium dioxide powders synthesized at different molar ratios of TiCl₄ and water vapor in the reactor are given in Table 1 below. Table 2 shows the specific surface areas of the powders produced, as well as the, rutile and anatase contents of those powders. Powders produced at the various molar ratios are designated as H1, H2, H3 and H4. TABLE 1 Aerosol Synthesis Condition of TiO₂ powder (Without gas phase dopant) Molar flow rate Powder Temperature, ° C. of TiCl₄ H₂O/TiCl₄ molar ratio H1 135 0.0026 14 H2 135 0.0015 20 H3 135 0.0007 33 H4 135 0.0013 49

TABLE 2 Characteristics of Titanium Dioxide powder Powder BET Surface Avg. particle Rutile content, Anatase content, No. Area m²/g) (nm*) wt % wt % H1 19 81 >99.9 <0.1 H2 22 69 87.0 13.0 H3 30 51 76.0 24.0 H4 33 46 21.0 79.0 *Based on BET surface area

EXAMPLE 2

Using the reactor and the analytical methods of Example 1, doped titanium dioxide was prepared as follows. The dopant ethanol kept at room temperature (28° C.) is introduced into the reactor through the third concentric tube. TiCl₄ vapor, water vapor and ethanol are mixed rapidly around the nozzle and form TiO₂ aerosol at near atmospheric pressure. Ethanol molar concentration in the range one to ten percent of the concentration of water vapor. Portions of the powders produced were heat treated in a conventional furnace. Powder was calcined at 500° C. for 3 hrs.

Titanium dioxide powders are synthesized at different molar ratios of H₂O/TiCl₄ in the reactor is given in Table 3 below. Table 4 show the specific surface areas of the powders produced as well as the rutile and anatase contents of these powders. Powders produced at the various molar ratios are designated as EH1, EH2 EH3 and EH4. TABLE 3 Aerosol Synthesis Condition of Titanium Dioxide powder (with gas phase dopant) H₂O/TiCl₄ Powder Temperature, ° C. molar ratio H₂O/TiCl₄ molar ratio EH1 137 14 7.0 EH2 137 20 6.0 EH3 137 33 3.5 EH4 137 49 3.0

TABLE 4 Characteristics of Titanium Dioxide powder Rutile Anatase Powder BET Surface content, content, No. Area (m²/g) Avg. particle size, nm* wt % wt % EH1 43.5 35 >99.9 <0.1 EH2 39.6 39 87.0 13.0 EH3 36.0 43 76.0 24.0 EH4 33.0 47 51.0 49.0 *Based on Bet surface area

TABLE 5 Comparison of rutile transition temperature observed with and without the dopant Titanium Dioxide Completion of particles Commence phase Obtained Ment of phase transformation Gas H₂O/ H₂O/ From vapor Transformation on to rutile, stream TiCl₄ Ethanol Phase on to rutile temperature. temp, ° C. molar ratio Molar ratio hydrolysis temperature. ° C. ° C.* 80 12 — Amorphous 300 600 80 12 7.4 Amorphous 150 400 137 15 — Anatase 800 1100 137 15 7.0 Anatase 500 700 Calcined duration: 3 hrs.

Table 5 illustrates the unique advantage of using dopant such as ethanol during the vapor phase hydrolysis step to achieve substantial reduction of the calcinations temperature required for obtaining titanium dioxide particles with rutile phase.

-   1. Nano and sub micron size titanium dioxide particles having the     rutile phase, anatase phase and mixtures there of could be     synthesized at temperatures less than 400° C. through vapor phase     reaction with TiCl₄ as the precursor. -   2. The other reactant involved in the process is water and ethanol,     which are of low cost and are environmentally green chemicals. -   3. The process is less energy consuming that the other available     process and involves negligible maintenance.

Prior art processes such as the chloride process developed for rutile manufacture (by Dupont) involves oxidation of titanium tetra chloride at a temperature of 1000-1200° C. The high purity oxygen is obtained through cryogenic air separation and the reaction is highly exothermic leading to release of large amount of energy (−130.98 KJ/mol at 1100° C.) which is removed from the reactor through heat exchangers containing cooling water. The high energy consumption and wastage in this process is due to

1. The energy for cryogenic separation of air into high purity oxygen

2. Pre-heating of TiCl₄ and oxygen to 1200° C.

3. Wastage of exothermic heat of reaction.

The process of the present invention does not require pure oxygen and the maximum reaction temperature in the aerosol reactor can be controlled to about 150° C. Thus reduced energy consumption is due to the absence of energy requirement of cryogenic oxygen separation and negligible preheat temperature of only 150° C. Additionally, there is no need for heat exchangers since the TiCl₄ hydrolysis reaction has a much lower exothermic heat of reaction (−20 kJ/mol at 150° C.).

The significance of the role played by ethanol to reduce the temperature of conversion of amorphous precursor to rutile is very clearly indicated in the XRD of the amorphous precursors. Specifically the XRD of the amorphous precursor synthesized with ethanol as dopant contains rutile fingerprints having shallow and broad peaks typical of non-crystallinity. However these features are absent in the XRD of amorphous precursors generated without ethanol. Without wishing to be bound by any theory, it is believed that the use of organic dopant influences the nucleation process of titanium dioxide powder by generating unique solid structures capable of being converted to rutile phase under mild calcination temperatures. 

1. A process for synthesis of ultrafine rutile phase titanium dioxide particles through vapor phase hydrolysis of titanium tetrachloride comprising the step of: (a) hydrolyzing a mixture of TiCl₄ and H₂O and a dopant in vapour phase in an aerosol reactor; (b) collecting amorphous or anatase titanium dioxide powder formed as dry powders; (c) calcining the dry powder to obtain rutile phase titanium dioxide.
 2. A process as claimed in claim 1 wherein the amorphous particles of titanium dioxide are calcined at a temperature in the range of 150 to 400° C. and for a period in the range of 1 to 4 hrs to generate rutile particles.
 3. A process as claimed in claim 1 wherein the dopant contains a carbon atom and is selected from the group consisting of an aliphatic alcohol, an aromatic hydrocarbon, and any mixture thereof.
 4. A process as claimed in claim 3 wherein the dopant is ethanol.
 5. A process as claimed in claim 1 wherein the molar concentration of the dopant is 1 to 10 based on the water vapour.
 6. A process as claimed in claim 1 wherein the reaction mixture contains from 1 to 10% ethanol on a molar basis based on TiCl₄.
 7. A process as claimed in claim 1 wherein the flow rate of TiCl₄ is in the range of 10 cm³/min to 200 cm³/min.
 8. A process as claimed in claim 1 wherein the TiCl₄ vapor concentration inside the reactor is in the range of 7×10⁻⁴ mol/min to 1×10⁻² mol/min.
 9. A process as claimed in claim 1 wherein the flow rate of water vapour is in the range of 240 to 1500 cm³/min, preferably from 500 to 1000 cm³/min.
 10. A process as claimed in claim 1 wherein the temperature at the exit of the aerosol reactor is maintained at less than 100° C. for obtaining titanium dioxide particles having anatase phase.
 11. A process as claimed in claim 1 wherein the aerosol reactor is externally heated in order to avoid particle coating on the walls through thermophoresis.
 12. A process as claimed in claim 1 wherein the aerosol reactor comprises of 3-tube concentric jet assembly wherein TiCl₄ is introduced into the innermost tube, dopant is introduced into the outermost tube and water vapor is introduced into the middle tube.
 13. A process as claimed in claim 12 wherein the 3-tube assembly comprises a concentric arrangement of three inconel tubes at the entrance of the aerosol reactor.
 14. A process as claimed in claim 12 wherein vapor phase TiCl₄ is introduced into a center tube of the three concentric inconel tubes.
 15. A process as claimed in claim 1 wherein the vapor phase TiCl₄ is formed by bubbling an inert gas through TiCl₄ liquid.
 16. A process as claimed in claim 1 wherein the inert gas is selected from the group consisting of argon, nitrogen, krypton, helium and any mixture thereof.
 17. A process as claimed in claim 1 wherein the molar ratio of water to titanium tetra chloride in the feed is in the range 10 to
 15. 18. A process as claimed in claim 1 wherein the water vapor is formed by bubbling air or inert gases through water under superheated condition.
 19. A process as claimed in claim 1 wherein the reactor wall temperature is from 200 to 450° C.
 20. A process as claimed in claim 1 wherein the rutile titanium dioxide particles formed have an average diameter in the range of from 25 to 150 nanometers.
 21. A vapor phase process for the synthesis of ultrafine rutile titanium dioxide powders carried out in an aerosol reactor comprising the steps of: (a) vaporizing a titanium chloride liquid, water and dopant such as ethanol separately for generating a reactant mixture; (b) hydrolyzing TiCl₄, H₂O and dopant in vapour phase mixture in a continuous aerosol reactor under non-isothermal conditions at temperature in the range 80 to 135° C.; (c) collecting amorphous and anatase phase titanium dioxide powder as dry powder; (d) calcining the titanium dioxide particles having the amorphous phase in the temperature ange of 150-400° C. and time duration in the range of 1 to 4 hrs. to obtain titanium dioxide particles with rutile phase. 